JPS63212934A - Photographic support - Google Patents

Abstract

PURPOSE:To increase the adhesive strength of a polyester film to a hydrophilic colloidal layer by exposing the film to corona discharge and coating it with an aq. dispersing polymer soln. contg. a fluorine-contg. surfactant and a water soluble polymer soln. CONSTITUTION:One side of a polyester film as a photographic support is exposed to corona discharge and coated with an aq. dispersing polymer soln. contg. a fluorine-contg. surfactant and a water soluble polymer soln. CF3(CF2)7- SO2-N(C2H5)-SO3H may be used as the fluorine-contg. surfactant, a styrene- butadiene copolymer soln. as the aq. dispersing polymer soln. and a gelatin soln. as the water soluble polymer soln. Since the polymer soln. contg. the fluorine-contg. surfactant is used, the adhesive strength of the photographic support to a covering substance is increased and the photographic characteristics can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Industrial Application Field The present invention relates to a support for a photographic polyester film for firmly adhering a photographic gelatin composition to a polyester film for a photographic light-sensitive material.

(B) Prior art and its problems It is well known that various methods have been tried in the past for subbing polyester films. but,
Polyester films generally have high crystallinity, are chemically insoluble, and are extremely hydrophobic, making it difficult to obtain good adhesion with hydrophilic photographic emulsion layers.

Conventional techniques that have been attempted to overcome these difficulties include chemical treatment, mechanical treatment, Discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment,
There are two methods: after performing the above treatments, a photographic emulsion is directly applied to obtain adhesive strength, and after these surface treatments, a subbing layer is provided and a photographic emulsion is applied on top of this. Of these, the latter method is more effective and widely practiced.

All of these surface treatments seem to make the surface of polyester, which was originally hydrophobic, more or less hydrophilic by creating polar groups, and as a result, the components contained in the undercoat layer become more or less hydrophilic. It is thought that the affinity between the polar groups of and the polyester surface increases.

As shown in JP-A-52-49019, JP-A-52-42114, and JP-A-52-104913, a method for applying the undercoat is to provide a layer that adheres well to the polyester film as a first layer, and then apply a layer as a second layer on top of that. There is a method of applying a hydrophilic resin layer, and a method of applying only one resin layer containing both a hydrophobic group and a hydrophilic group. For example, copolymers starting from vinylidene chloride, vinyl chloride, methacrylic acid and acrylic acid and their esters, maleic anhydride, styrene, butadiene, etc.
4270 and JP-A-51-30274, grafted gelatin or nitrocellulose is dissolved in an organic solvent and a compound such as P-chlorophenol or resorcinol, which is a solvent or swelling agent for the support film, is added. A method is used in which a liquid is applied to a support film.

However, in the processing methods using these solvent-based subbing liquids, when the subbing liquid is applied and dried, vapors of organic solvents, which are harmful to the environment, are emitted, which often causes problems in the work. For this reason, it is necessary to provide a solvent recovery device at great expense.

In particular, the inclusion of the solvent or swelling agent for the support film in the subbing liquid not only releases harmful vapors, but also causes the film to lose its transparency and impairs the flatness of the film, which significantly impairs the finished quality. Aggravating adverse effects often occur.

Therefore, as an undercoat processing method that improves this drawback, a method has been adopted in which an aqueous dispersion containing various heptad copolymers is used as a subbing liquid instead of a solvent-based subbing liquid.

For example, a subbing method using an aqueous dispersion containing a butadiene-styrene copolymer and a subbing method containing a vinylidene copolymer are known. However, in order to provide excellent adhesion by applying an aqueous dispersion containing a copolymer onto a hydrophobic film, it is difficult to select the type of aqueous dispersion and processing conditions to ensure sufficient adhesion. difficult to do.

(C) Object of the Invention The first object of the invention is to provide a photographic support having strong adhesive strength between a polyester film and a photographic hydrophilic colloid layer.

A second object of the present invention is to provide a photographic support that does not require the use of swelling or dissolving agents for polyester, and therefore does not emit harmful organic solvents into the exhaust gas or exhaust air, thereby causing no pollution. It is to be.

A third object of the present invention is to provide a photographic support with excellent flatness and transparency.

A fourth object of the present invention is to provide a photographic support having a subbing layer comprising a subbing composition that can be stably and easily produced.

A fifth object of the present invention is to provide a photographic support having a subbing layer made of the undercoat composition having good storage stability.

A sixth object of the present invention is to provide a photographic support that can be stably manufactured without causing fluctuations in undercoat performance even when the coating and drying conditions in the undercoat coating process vary.

The seventh object of the present invention is to provide various photographic hydrophilic colloid layers,
In particular, it is an object of the present invention to provide a photographic support that does not have an adverse effect on the photographic emulsion layer.

(D) Structure of the Invention The present inventors focused on the surfactants used in the subbing coating process and, as a result of extensive research, developed an aqueous dispersion polymer liquid containing a fluorine-containing surfactant.

We have also found that a photographic polyester film support that can improve the above-mentioned drawbacks can be obtained by coating at least one surface of a photographic polyester film after corona discharge treatment with a water-soluble polymer solution.

Examples of the fluorine-containing surfactant used in the present invention include, for example, Japanese Patent Publication No. 47-9303, Japanese Patent Publication No. 48-43130, German Published Patent Application No. 950,121, Japanese Patent Publication No. 1,961,
638, JP-A-46-7781, JP-A-48-44182
, No. 50-113221, U.S. Patent No. 3,589,9
No. 06, Japanese Patent Application No. 53-18399, etc. can be referred to. Preferred are anionic or amphoteric organic fluorine-containing compounds. Some specific examples are shown below, but it goes without saying that the invention is not limited to these.

CFa (CF2)e -COONH4CF3 (C
F2)? -3O3K CF3 (CF, ) 1l-CI2-0303Na, etc.

The amount of fluorine-containing surfactant added is approximately 0.0 per 11 coating liquid.
The amount ranges from 0.01 to 2 g, preferably from 0.005 to 1 g, but amounts outside this range may also be used.

Generally, photographic materials using a polyester film as a support have a structure in which a multilayer aqueous colloid solution is coated on the support, and the selection of the surfactant in each layer is important.

Therefore, the present inventors focused on the combination of surfactants used in the subbing layer of the polyester film support and the photographic light-sensitive emulsion layer, and arrived at the present invention = As a component of the subbing layer of the polyester film support. In recent years, aqueous dispersions of synthetic polymers have been widely used, but these are mainly synthesized by emulsion polymerization.

Preferred are water-dispersible polymers with a low softening point, particularly styrene/butadiene copolymers, styrene/acrylic ester copolymers, acrylonitrile/butadiene copolymers, acrylonitrile/acrylic ester copolymers, Vinylidene chloride copolymer, vinylidene chloride/acrylic acid ester copolymer, vinylidene chloride/acrylonitrile copolymer, vinyl chloride/vinylidene chloride copolymer, vinyl chloride/vinyl acetate copolymer, vinyl chloride/acrylic acid ester copolymer Examples include polymers, acrylic ester copolymers, chloroprene copolymers, ethylene copolymers, urethane copolymers, and the like.

In order to obtain a good subbing layer, in addition to the combination of surfactants used in the subbing layer and emulsion layer, for example, using the same type of surfactant as in the subbing layer, it is necessary to Research has revealed that it is important to achieve good results in dispersing aqueous dispersions of synthetic polymers synthesized by emulsion polymerization. The details will be shown in Examples, but it has been found that the surfactant used in the present invention gives good results in dispersing synthetic polymers. Furthermore, it has good compatibility with aqueous polymers such as gelatin, polyvinyl alcohol, polyacrylamide, carboxymethyl cellulose, etc., and is particularly effective when mixing these aqueous polymers with aqueous dispersions of synthetic polymers. I also understood. Although it is possible to use other types of surfactants in addition to the fluorine-containing surfactant, it is desirable to limit the amount to 50% or less of the total surfactants in the same layer.

Furthermore, other additives such as antihalation dyes, hardeners, matting agents or swelling agents, and etching agents may be added as necessary to the extent that no hindrance is caused.

On the other hand, the advantages of corona discharge treatment are that the treatment time is extremely short and there is no need to handle dangerous oxidizing chemicals or worry about waste contamination. Corona discharge treatment is a treatment method that utilizes a device such as a corona discharge device that easily performs corona treatment in the presence of gas or under reduced pressure vacuum between at least a pair of electrodes, such as a corona discharge device, before coating and drying a photographic polyester film. , the processing conditions can be arbitrarily selected together with the processing equipment.

The subbing composition of the present invention can be applied by various coating methods including dip coating, air knife coating, extrusion coating, and curtain coating. Also, two or more layers can be applied simultaneously or separately, if desired.

(E) Examples The present invention will be specifically explained by examples, but the embodiments of the present invention are not limited thereby.

The evaluation of the adhesive strength between the support of the photographic polyester film and the emulsion layer in the following Examples is as follows.

(1) Adhesion test during drying Use a razor to make shallow scratches on the emulsion surface of the dry film in a mesh pattern, press a well-adhering cellophane tape onto the scratches, and peel off the scratches instantly. In this method, the peeled area is 0.
○ mark for ~5%, Δ mark for 5~25%, 30~
100% is marked with an X.

(2) Adhesion test during wet processing PQ developer (pH = 10.5) 1 sample at 35°C
Soak for a minute, then make scratches on the surface of the emulsion film under running water in the shape of base marks using an iron pen, and rub the scratched area with a piece of rubber. If the emulsion layer does not spread beyond the scratch, mark it with an ○. Maximum spread is within 3M with Δ mark, and X indicates that the spread is larger than the scratch and the peeling is large.
Mark it as a mark.

Example 1 The surface of a photographic polyethylene terephthalate film with a thickness of 100IIIt was subjected to corona discharge treatment, and the discharge output was 600.
W, electrode gap 1.6, film speed 20TrL/
minutes), a subbing composition of the present invention having the following composition was coated with an air knife coater to give a luminosity of 207! Coated and dried.

Coating liquid 1 When a normal silver iodobromide gelatin emulsion was applied to the surface of the coating in an amount of 3 g of silver and 4 g of gelatin per square meter and dried,
The adhesion between the emulsion layer and the support was evaluated as good with an O mark both when dry and when wet.

Example 2 After the surface of a photographic polyethylene terephthalate film having a thickness of 175 IIlt was subjected to corona discharge treatment in the same manner as in Example 1, a subbing composition of the present invention having the following composition was coated with a thickness of 20 m per square using an air knife coater. Dry.

Coating liquid 2 1 Styrene maleic anhydride copolymer 75dA gelatin-silver halide emulsion was coated on the surface of the 75d in the same manner as in Example 1 and dried.
The evaluation was good with an O mark both when wet.

Example 3 After the surface of a photographic polyethylene terephthalate film with a thickness of 175 mm was subjected to corona discharge treatment in the same manner as in Example 1,
A subbing composition of the present invention having the following composition was coated and dried for 20 d with an air knife coater.

Coating Solution 3 After coating and drying in the same manner as in Example 1, the adhesion between the emulsion layer and the support was evaluated as good with an O mark both when dry and when wet.

Example 4 After the surface of a photographic polyethylene terephthalate film having a thickness of 100IIIt was subjected to corona discharge treatment in the same manner as in Example 1, a subbing composition of the present invention having the following composition was coated with an air knife coater for 20 rds and dried. did.

Coating Solution 4 A backing layer containing ordinary gelatin and a matting agent dye was applied to the surface of the coating in an amount of 4 g of glossy gelatin per square meter and dried. The adhesion between the backing layer and the support was evaluated both when dry and when wet. was good with an O mark.

Example 5 Exemplified compound (2) instead of exemplary compound (5) in coating liquid 2
Coating liquid 5 was prepared using the following formula, coating liquid 6 was prepared using exemplary compound (7), and coating liquid 7 was prepared using exemplary compound (9), respectively. After corona discharge treatment was applied to the surface of a photographic polyethylene terephthalate film under the same conditions as in Example 1, these coating liquids were coated with an air knife coater to coat the surface of a photographic polyethylene terephthalate film at a rate of 2.
It was coated and dried to obtain a subbing film. When a silver iodobromide emulsion was applied to the surface of the support in an amount of 3 g of silver and 4 g of gelatin per square meter and dried, the adhesion between the emulsion layer and the support was confirmed.
The evaluation was good with an O mark both when dry and when wet.

Comparative Example 1 A coating liquid was prepared as follows. A photographic film was prepared in the same manner as in Example 3.

Coating liquid 8 Same as coating liquid 3 except that comparative compound (1) was used instead of exemplified compound (5).

Coating liquid 9 Same as coating liquid 3 except that comparative compound (2) was used instead of exemplified compound (5).

Coating Solution 10 Same as Coating Solution 3 except that Comparative Compound (3) was used instead of Exemplary Compound (5) All three of these photographic films had adhesion evaluations of O to Δ when dry, and when wet. So it was X.

Comparative compounds (1) Saponin (2) Sodium diethylhexyl sulfosuccinate (3)
) Sodium naphthalene sulfonate Comparative Example 2 The coating solutions of Examples 1, 2, 3, and 4 were applied to the surface of a photographic polyethylene terephthalate film that was not subjected to corona discharge treatment using an air knife coater. Separately, 20 m of light was applied and dried.

When a silver iodobromide emulsion was coated on the surface and dried in the same manner as in Example 1, the adhesion between the emulsion layer and the support was evaluated as O when dry.
However, the wet adhesion evaluation was marked with an X, indicating that it could not be put to practical use.

(F) Effect of the invention As is clear from the above examples and comparative examples, a water-based dispersion polymer solution containing a fluorine-containing surfactant or a water-soluble polymer solution is applied to the surface of a photographic polyethylene terephthalate film treated by corona discharge treatment. A photographic support coated with a molecular solution exhibits excellent adhesion to coating substances and excellent photographic properties.

Claims (1)

[Claims] A photographic support characterized in that an aqueous dispersion polymer solution and/or water-soluble polymer solution containing a fluorine-containing surfactant is coated on the surface of a photographic polyethylene terephthalate film whose at least one side has been treated by corona discharge treatment. body.